Complexes of the type [PtCl(N-N)(eta(1)-CH2CH2OR)], N-N = diimine ligand, R = alkyl, were generally considered to be indefinitely stable, both in solution and in the solid state. Unexpectedly we found that complexes of the type [PtCl(Me(2)phen)(eta(1)-CH2CH2OR)], Me(2)phen 2,9-dimethyl-1,10-phenatroline, R = alkyl, undergo spontaneous decomposition, to give the corresponding vinyl-ether, CH2 = CHOR. Decomposition pathway studies suggest a pseudo-Wacker type mechanism (beta H- shift process) activated by sterical hindrance in the Pt(II) coordination plane, due to the Me(2)phen ligand sterically induced distortions in the Pt(II) coordination plane. A new useful synthetic pathway to access valuable and low toxic alkyl-vinyl-ethers is here reported.
Alkyl-vinyl-ethers from alcoholic substrates and the Zeise's salt, via square planar [PtCl(N-N)(eta(1)-CH2CH2OR)] complexes
BENEDETTI, MICHELE
Primo
;CICCARELLA, GiuseppePenultimo
;FANIZZI, Francesco Paolo
Ultimo
2012-01-01
Abstract
Complexes of the type [PtCl(N-N)(eta(1)-CH2CH2OR)], N-N = diimine ligand, R = alkyl, were generally considered to be indefinitely stable, both in solution and in the solid state. Unexpectedly we found that complexes of the type [PtCl(Me(2)phen)(eta(1)-CH2CH2OR)], Me(2)phen 2,9-dimethyl-1,10-phenatroline, R = alkyl, undergo spontaneous decomposition, to give the corresponding vinyl-ether, CH2 = CHOR. Decomposition pathway studies suggest a pseudo-Wacker type mechanism (beta H- shift process) activated by sterical hindrance in the Pt(II) coordination plane, due to the Me(2)phen ligand sterically induced distortions in the Pt(II) coordination plane. A new useful synthetic pathway to access valuable and low toxic alkyl-vinyl-ethers is here reported.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
